U.S. patent number 10,994,563 [Application Number 15/556,644] was granted by the patent office on 2021-05-04 for method for coloring an optical element in a non-uniform linear pattern.
This patent grant is currently assigned to Transitions Optical, Inc.. The grantee listed for this patent is Transitions Optical, Inc.. Invention is credited to William D. Carpenter, Jennine M. Frease.
United States Patent |
10,994,563 |
Frease , et al. |
May 4, 2021 |
Method for coloring an optical element in a non-uniform linear
pattern
Abstract
A method for coloring an optical element in a non-uniform linear
pattern is provided. The method includes (a) preparing at least one
colorant composition containing at least one photochromic material;
(b) depositing the colorant composition on at least one surface of
the optical element in a controlled, predetermined pattern using an
inkjet printing apparatus to provide a linearly gradient color
pattern on the optical element when the optical element is exposed
to actinic radiation; and (c) drying the colorant composition on
the surface of the optical element. An optical element prepared by
the method also is provided.
Inventors: |
Frease; Jennine M. (St.
Petersburg, FL), Carpenter; William D. (Pinellas Park,
FL) |
Applicant: |
Name |
City |
State |
Country |
Type |
Transitions Optical, Inc. |
Pinellas Park |
FL |
US |
|
|
Assignee: |
Transitions Optical, Inc.
(Pinellas Park, FL)
|
Family
ID: |
1000005528293 |
Appl.
No.: |
15/556,644 |
Filed: |
March 10, 2015 |
PCT
Filed: |
March 10, 2015 |
PCT No.: |
PCT/US2015/019690 |
371(c)(1),(2),(4) Date: |
September 08, 2017 |
PCT
Pub. No.: |
WO2016/144332 |
PCT
Pub. Date: |
September 15, 2016 |
Prior Publication Data
|
|
|
|
Document
Identifier |
Publication Date |
|
US 20180050549 A1 |
Feb 22, 2018 |
|
Current U.S.
Class: |
1/1 |
Current CPC
Class: |
B29D
11/00923 (20130101); B41M 3/003 (20130101); B29D
11/00653 (20130101); B41M 5/0047 (20130101); B41M
5/0064 (20130101); G02C 7/105 (20130101) |
Current International
Class: |
B29D
11/00 (20060101); G02C 7/10 (20060101); B41M
5/00 (20060101); B41M 3/00 (20060101) |
Field of
Search: |
;427/162 |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
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1392834 |
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Jan 2003 |
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CN |
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1493015 |
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Apr 2004 |
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CN |
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102033328 |
|
Apr 2011 |
|
CN |
|
2881230 |
|
Jul 2006 |
|
FR |
|
1 520 099 |
|
Aug 1978 |
|
GB |
|
2008279425 |
|
Nov 2008 |
|
JP |
|
2012173675 |
|
Sep 2012 |
|
JP |
|
9420581 |
|
Sep 1994 |
|
WO |
|
2013112328 |
|
Aug 2013 |
|
WO |
|
Primary Examiner: Burkhart; Elizabeth A
Attorney, Agent or Firm: The Webb Law Firm
Claims
The invention claimed is:
1. A method for coloring an optical element in a non-uniform linear
pattern, the method comprising: (a) preparing at least one colorant
composition comprising at least one photochromic material
comprising a photochromic compound selected from the group
consisting of pyrans, spiropyrans, oxazines, spiroxazines,
fulgides, fulgimides, metallic dithizonates, diarylethenes, and
mixtures thereof; (b) depositing the colorant composition on at
least one surface of the optical element in a controlled
predetermined pattern using an inkjet printing apparatus so as to
provide a linearly gradient color pattern on the optical element
upon exposure of the optical element to actinic radiation, wherein
(1) the predetermined pattern is formed by deposition of multiple
colorant compositions using an ink jet apparatus comprised of
multiple print heads, and each print head is provided with a
different colorant composition, or (2) the predetermined pattern is
formed by deposition of a single colorant composition deposited in
one or more successive layers using an ink jet apparatus comprising
a single print head; and (c) drying the colorant composition on the
surface of the optical element.
2. The method of claim 1, wherein the optical element comprises a
substrate having a uniform tinted color prior to deposition of the
colorant composition.
3. The method of claim 1, wherein the colorant composition further
comprises at least one polymeric component.
4. The method of claim 1, wherein the inkjet apparatus is comprised
of multiple print heads, where each print head is provided with (i)
a different colorant composition, and (ii) optionally, a
composition free of photochromic material, and wherein each
composition is deposited on the surface of the optical element in a
predetermined pattern so as to provide a linearly gradient color
pattern which varies in hue and/or color density from one area of
the optical element to another area of the optical element upon
exposure of the optical element to actinic radiation.
5. The method of claim 1, wherein the inkjet apparatus is comprised
of multiple print heads, where each print head is provided with a
different colorant composition, and wherein each composition is
deposited on the surface of the optical element in a predetermined
pattern so as to provide a linearly gradient color pattern which
varies in hue from one area of the optical element to another area
of the optical element upon exposure of the optical element to
actinic radiation.
6. The method of claim 1, wherein the colorant composition is
heated within the inkjet apparatus prior to depositing the colorant
composition onto at least one surface of the optical element.
7. The method of claim 1, wherein the optical element is selected
from the group consisting of lenses, windows, display elements,
goggles, visors, face shields, automotive transparencies, aerospace
transparencies, and wearable displays.
8. The method of claim 7, wherein the optical element is an
ophthalmic lens.
9. The method of claim 7, wherein the optical element is a lens,
and the linearly gradient color pattern varies in hue and/or color
density from the bottom of the lens to the top of the lens upon
exposure of the lens to actinic radiation.
10. The method of claim 9, wherein, upon exposure of the lens to
actinic radiation, the gradient color pattern has a higher percent
light transmittance at the bottom of the lens than at the top of
the lens.
11. The method of claim 1, wherein the colorant composition
comprises a curable composition comprising at least one
photochromic dye and at least one polymeric component.
12. The method of claim 1, further comprising leveling the colorant
composition during the depositing step (b) or immediately
thereafter, but prior to the drying step (c).
13. The method of claim 12, wherein the leveling comprises
vibrating the optical element.
14. The method of claim 13, wherein the leveling comprises
vibrating the optical element linearly.
15. The method of claim 14, wherein the leveling comprises
vibrating the optical element linearly along one axis.
16. The method of claim 14, wherein the leveling comprises
vibrating the optical element linearly along two axes.
17. The method of claim 14, wherein the leveling comprises
vibrating the optical element linearly in one plane.
18. The method of claim 1, wherein the inkjet printing apparatus is
a piezo-electric inkjet printing apparatus.
19. The method of claim 1, wherein the inkjet printing apparatus is
a thermal inkjet printing apparatus.
Description
CROSS-REFERENCE TO RELATED APPLICATION
This application is the United States national phase of
International Application No. PCT/US2015/019690 filed Mar. 10,
2015, which is incorporated herein by reference in its
entirety.
FIELD OF THE INVENTION
The present invention is directed to a method for preparing a
colored optical element in a non-uniform linear pattern, such as a
linearly gradient color pattern, using an inkjet printing
apparatus.
BACKGROUND OF THE INVENTION
Gradient tinting methods are known for use in coloring optical
elements, such as lenses. The gradient tinting effect provides a
functional advantage in that the lens generally has a higher color
density at the top of the lens for improved distance viewing with
less color density at the bottom of the lens, and an aesthetic
effect for fashion and style.
Further, there are well known methods for applying a photochromic
composition to optical elements. For example, photochromic
materials may be incorporated into the substrate components used to
form the optical element. Alternatively, the photochromic materials
may be applied to the surface of the optical element and permitted
to penetrate into the surface region (known as imbibition).
Additionally, the photochromic material can be applied to the
optical element as a coating by known methods, such as spin
coating, dip coating, spray coating, and the like.
Methods have been disclosed to achieve a gradient photochromic
optical element. Generally, gradient tinting of eyewear lenses is
accomplished by dipping or submerging the lens into a dye bath.
This process requires more precise and reproducible processing than
is required for solid tinting or coloring. Moreover, some optical
substrates, such as polycarbonate lens material, absorb dyes very
poorly. While methods have been developed to overcome these
processing difficulties, such methods often require additional
manufacturing steps, thus adding additional manufacturing
costs.
Accordingly, it would be desirable to provide a cost-effective
method of preparing a gradient photochromic optical element where a
photochromic composition can be applied in a controlled and
predetermined gradient color pattern (upon exposure to actinic
radiation) to the surface of the optical element.
SUMMARY OF THE INVENTION
The present invention provides a method for coloring an optical
element in a non-uniform linear pattern. The method comprises (a)
preparing at least one colorant composition comprising at least one
photochromic material; (b) depositing the colorant composition on
at least one surface of the optical element in a controlled,
predetermined pattern using an inkjet printing apparatus to provide
a linearly gradient color pattern on the optical element when the
optical element is exposed to actinic radiation; and (c) drying the
colorant composition on the surface of the optical element. An
optical element prepared by the method of the present invention
also is provided.
DETAILED DESCRIPTION OF THE INVENTION
Unless otherwise indicated, all ranges or ratios disclosed herein
are to be understood to encompass any and all sub-ranges or
sub-ratios subsumed therein. For example, a stated range or ratio
of "1 to 10" should be considered to include any and all sub-ranges
between (and inclusive of) the minimum value of 1 and the maximum
value of 10. That is, all sub-ranges or sub-ratios beginning with a
minimum value of 1 or more and ending with a maximum value of 10 or
less, such as, but not limited to, 1 to 6.1; 3.5 to 7.8; and 5.5 to
10.
As used herein and in the claims, the term "polymer" and like
terms, such as "polymeric", means homopolymers (prepared from a
single monomer), copolymers (prepared from two or more different
monomers), and graft polymers, including but not limited to comb
graft polymers, star graft polymers, and dendritic graft
polymers.
As used in this specification and the appended claims, the articles
"a", "an", and "the" include plural referents unless expressly and
unequivocally limited to one referent.
Additionally, for the purposes of this specification, unless
otherwise indicated, all numbers expressing quantities of
ingredients, reaction conditions, and other properties or
parameters used in the specification are to be understood as being
modified in all instances by the term "about". Accordingly, unless
otherwise indicated, it should be understood that the numerical
parameters set forth in the following specification and attached
claims are approximations. At the very least, and not as an attempt
to limit the application of the doctrine of equivalents to the
scope of the claims, numerical parameters should be read in light
of the number of reported significant digits and the application of
ordinary rounding techniques.
As previously mentioned, the present invention is directed to a
method for coloring an optical element in a non-uniform linear
pattern, such as a linearly gradient color pattern. For purposes of
the present invention, a "linearly gradient color pattern" is
achieved through the deposition via inkjet printing techniques, of
a photochromic composition comprising photochromic dyes (which are
described in further detail herein below) to create a gradual,
visually discernible variation in hue and/or color density over an
area of the optical element when the optical element is exposed to
actinic radiation. The gradual variation in hue and/or color
density occurs across the surface of the optical element in one
direction. For example, when the optical element is a lens, the
variation in hue and/or color density can occur from the bottom of
the lens to top of the lens. That is, the deposition of a
particular composition occurs across the lens from one side to the
other such that the variation in hue and/or color density occurs
from the bottom to the top or vice versa. The term "hue" as used
herein means pure color expressed in terms such as "green", "red"
or "magenta"; and includes mixtures of two pure colors like
"red-yellow" (i.e., "orange") or "yellow-green". The term "color
density" as used herein means, upon exposure to actinic radiation,
optical density of an area of the optical element surface printed
with the colorant composition. A higher color density results in a
lower percent light transmittance. For purposes of this invention,
the bottom of the lens is closest to the lens wearer's cheekbone,
and the top of the lens is closest to the lens wearer's forehead.
This linearly gradient color pattern should be differentiated from
radially gradient color patterns known in the art, e.g., those used
in connection with lenses, wherein color density varies radially
outward from a center point to the outer perimeter of the lens.
The optical element can be any of those known in the art.
Generally, the optical element is selected from the group
consisting of lenses, windows, display elements, goggles, visors,
face shields, automotive transparencies, e.g., sunroofs and light
covers, aerospace transparencies, and wearable transparencies.
Further, the optical element used in the method of the present
invention can be substantially transparent, or it may possess a
uniform color (e.g., the optical element may be tinted), prior to
deposition of the aforementioned colorant composition.
In a particular embodiment, the optical element is a lens. The lens
can be an ophthalmic lens. As used herein, the term "optical" means
pertaining to or associated with light and/or vision. As used
herein, the term "ophthalmic" means pertaining to or associated
with the eye and vision. Non-limiting examples of ophthalmic
elements include corrective and non-corrective (piano) lenses,
including single vision or multi-vision lenses, which may be either
segmented or non-segmented multi-vision lenses (such as, but not
limited to, bifocal lenses, trifocal lenses, and progressive
lenses), as well as other elements used to correct, protect, or
enhance (cosmetically or otherwise) vision, including without
limitation, contact lenses, intra-ocular lenses, magnifying lenses,
and protective lenses or visors. As used herein, the term "display"
means the visible or machine-readable representation of information
in words, numbers, symbols, designs, or drawings. Non-limiting
examples of display elements and devices include screens and
monitors. As used herein, the term "window" means an aperture
adapted to permit the transmission of radiation therethrough.
The optical element can comprise any of the optical substrates well
known in the art. The substrate may comprise a polymeric organic
material chosen from thermosetting polymeric organic materials,
thermoplastic polymeric organic materials, or a mixture of such
polymeric organic materials. The polymeric organic material can be
chosen from poly(C.sub.1-C.sub.12 alkyl methacrylates),
poly(oxyalkylene dimethacrylates), poly(alkoxylated phenol
methacrylates), cellulose acetate, cellulose triacetate, cellulose
acetate propionate, cellulose acetate butyrate, poly(vinyl
acetate), poly(vinyl alcohol), poly(vinyl chloride),
poly(vinylidene chloride), thermoplastic polycarbonates,
polyesters, polyurethanes, polythiourethanes,
polysulfithiourethanes, poly(urea-urethane), poly(ethylene
terephthalate), polystyrene, poly(alpha methylstyrene),
copoly(styrene-methylmethacrylate), copoly(styrene-acrylonitrile),
polyvinyl butyral or polymers prepared from bis(allyl carbonate)
monomers, polyfunctional acrylate monomers, polyfunctional
methacrylate monomers, diethylene glycol dimethacrylate monomers,
diisopropenyl benzene monomers, ethoxylated bisphenol A
dimethacrylate monomers, ethylene glycol bismethacrylate monomers,
poly(ethylene glycol) bismethacrylate monomers, ethoxylated phenol
bismethacrylate monomers, alkoxylated polyhydric alcohol
polyacrylate monomers, styrene monomers, urethane acrylate
monomers, glycidyl acrylate monomers, glycidyl methacrylate
monomers, diallylidene pentaerythritol monomers, or mixtures of
such monomers.
Substrates suitable for use in the preparation of optical elements
of the present invention typically demonstrate a refractive index
of at least 1.55 and can include non-plastic substrates, such as
glass. More often, substrates commonly used in optical applications
are used, including polyol(allyl carbonate) monomers, e.g., allyl
diglycol carbonates such as diethylene glycol bis(allyl carbonate),
which monomer is sold under the registered trademark CR-39 by PPG
Industries, Inc.; poly(urea)urethane polymers, which are prepared,
for example, by the reaction of a polyurethane prepolymer and a
diamine curing agent, a composition for one such polymer being sold
under the registered trademark TRIVEX by PPG Industries, Inc.;
polyol(meth)acryloyl terminated carbonate monomer; diethylene
glycol dimethacrylate monomers; ethoxylated phenol methacrylate
monomers; diisopropenyl benzene monomers; ethoxylated trimethylol
propane triacrylate monomers; ethylene glycol bismethacrylate
monomers; poly(ethylene glycol) bismethacrylate monomers; urethane
acrylate monomers; poly(ethoxylated bisphenol A dimethacrylate);
poly(vinyl acetate); poly(vinyl alcohol); poly(vinyl chloride);
poly(vinylidene chloride); polyethylene; polypropylene;
polyurethanes; polythiourethanes; thermoplastic polycarbonates,
such as the carbonate-linked resin derived from bisphenol A and
phosgene, one such material being sold under the registered
trademark LEXAN by Sabic Global Technologies; polyesters, such as
the material sold under the registered trademark MYLAR by Dupont
Teijin Films; poly(ethylene terephthalate); polyvinyl butyral;
poly(methyl methacrylate), such as the material sold under the
registered trademark PLEXIGLAS by Arkema France Corporation, and
polymers prepared by reacting polyfunctional isocyanates with
polythiols or polyepisulfide monomers, either homopolymerized or
co- and/or terpolymerized with polythiols, polyisocyanates,
polyisothiocyanates, and, optionally, ethylenically unsaturated
monomers or halogenated aromatic-containing vinyl monomers. Also
contemplated are copolymers of such monomers and blends of the
described polymers and copolymers with other polymers, e.g., to
form interpenetrating network products.
As mentioned above, in the method of the present invention, a
colorant composition is prepared and deposited on at least one
surface of the optical element, such as any of those previously
described. The colorant composition comprises a photochromic
material. Photochromic materials useful in the method of the
present invention comprise at least one photochromic compound
selected from the group consisting of pyrans, spiropyrans,
oxazines, spiroxazines, fulgides, fulgimides, metallic
dithizonates, diarylethenes, and mixtures thereof. Specific but
non-limiting examples of suitable photochromic materials can
include indeno-fused naphthopyrans, naphtho[1,2-b]pyrans,
naphtho[2,1-b]pyrans, spirofluoroeno[1,2-b]pyrans,
phenanthropyrans, quinolinopyrans, fluoroanthenopyrans,
spiropyrans, benzoxazines, naphthoxazines,
spiro(indoline)naphthoxazines, spiro(indoline)pyridobenzoxazines,
spiro(indoline)fluoroanthenoxazines, spiro(indoline)quinoxazines,
fulgides, fulgimides, diarylethenes, diarylalkylethenes, and
diarylalkenylethenes.
As used herein, the term "photochromic" and similar terms, such as
"photochromic compound", includes thermally reversible photochromic
compounds, and non-thermally reversible photochromic compounds, and
mixtures thereof. The term "thermally reversible photochromic
compounds/materials" as used herein means compounds/materials
capable of converting from a first state (i.e., unactivated or
clear state) to a second state (i.e., activated or colored state)
in response to actinic radiation, and reverting back to the first
state in response to thermal energy. The term "non-thermally
reversible photochromic compounds/materials" as used herein means
compounds/materials capable of converting from a first state (i.e.,
clear or unactivated state) to a second state (i.e., activated or
colored state) in response to actinic radiation; and reverting back
to the first state in response to actinic radiation of
substantially the same wavelength(s) as the absorption(s) of the
colored state.
In addition to the photochromic material, the colorant composition
can comprise one or more polymeric components. Examples of suitable
polymeric components can include, but are not limited to, the
following polymers or precursors thereof: polyvinyl alcohol,
polyvinyl chloride, polyurethane, polyacrylate, and
polycaprolactam. The colorant composition can be a thermoplastic
composition or a thermosetting composition. In a particular
embodiment of the present invention, the colorant composition can
be a curable composition comprising a photochromic material, a
curable resin composition, and, optionally, a solvent.
The curable resin composition typically includes a first reactant
(or component) having functional groups, e.g., hydroxyl functional
polymer reactant; and a second reactant (or component) that is a
crosslinking agent having functional groups that are reactive
towards and that can form covalent bonds with the functional groups
of the first reactant. The first and second reactants of the
curable resin composition can each independently include one or
more functional species, and are each present in amounts sufficient
to provide cured coatings having a desirable combination of
physical properties, e.g., smoothness, solvent resistance, and
hardness.
Examples of curable resin compositions that can be used with the
curable resin compositions include, but are not limited to, curable
resin compositions that include an epoxide functional polymer, such
as (meth)acrylic polymers containing residues of
glycidyl(meth)acrylate, and an epoxide reactive crosslinking agent
(e.g., containing active hydrogens, such as hydroxyls, thiols, and
amines); curable resin compositions that include active hydrogen
functional polymer, such as hydroxy functional polymer and capped
(or blocked) isocyanate functional crosslinking agent; and curable
resin compositions that include active hydrogen functional polymer,
such as hydroxy functional polymer, and aminoplast crosslinking
agent.
With some aspects of the present invention, the colorant
composition comprises a photochromic material and a curable resin
composition which is a curable urethane (or polyurethane) resin
composition. In addition to the photochromic material, such a
curable urethane composition typically contains an active hydrogen
functional polymer, such as an amino functional polymer or a
hydroxy functional polymer; and a capped (or blocked) isocyanate
functional crosslinking agent. Active hydrogen functional polymers
are well known in the art. Hydroxy functional polymers that can be
used in such compositions include, but are not limited to,
art-recognized hydroxy functional vinyl polymers, hydroxy
functional polyesters, hydroxy functional polyurethanes, and
mixtures thereof.
Vinyl polymers having active hydrogen groups, such as hydroxy
functional groups, can be prepared by free radical polymerization
methods that are known to those of ordinary skill in the art. With
some aspects of the present invention, a hydroxy functional vinyl
polymer is prepared from a majority of (meth)acrylate monomers and
is referred to herein as a "hydroxy functional (meth)acrylic
polymer".
Hydroxy functional polyesters useful in curable coating
compositions that include capped isocyanate functional crosslinking
agents can be prepared by art-recognized methods. Typically, diols
and dicarboxylic acids or diesters of dicarboxylic acids are
reacted in a proportion such that the molar equivalents of hydroxy
groups is greater than that of carboxylic acid groups (or esters of
carboxylic acid groups) with the concurrent removal of water or
alcohols from the reaction medium.
Hydroxy functional urethanes can be prepared by art-recognized
methods. Typically, one or more difunctional isocyanates are
reacted with one or more materials having two active hydrogen
groups (e.g., diols or dithiols), such that the ratio of active
hydrogen groups to isocyanate groups is greater than 1, as is known
to the skilled artisan.
By "capped (or blocked) isocyanate crosslinking agent" is meant a
crosslinking agent having two or more capped isocyanate groups that
can decap (or deblock) under cure conditions, e.g., at elevated
temperature, to form free isocyanate groups and free capping
groups. The free isocyanate groups formed by decapping of the
crosslinking agent are typically capable of reacting and forming
substantially permanent covalent bonds with the active hydrogen
groups of the active hydrogen functional polymer (e.g., with the
hydroxy groups of a hydroxy functional polymer).
It is desirable that the capping group of the capped isocyanate
crosslinking agent not adversely affect the curable coating
composition upon decapping from the isocyanate (i.e., when it
becomes a free capping group). For example, it is desirable that
the free capping group neither become trapped in the cured film as
gas bubbles nor excessively plasticize the cured film. Capping
groups useful in the present invention typically have the
characteristics of being non-fugitive or capable of escaping
substantially from the forming coating prior to its
vitrification.
Classes of capping groups of the capped isocyanate crosslinking
agent can be selected from, include, but are not limited to hydroxy
functional compounds, e.g., linear or branched C.sub.2-C.sub.8
alcohols, ethylene glycol butyl ether, phenol and p-hydroxy
methylbenzoate; 1H-azoles, e.g., 1H-1,2,4-triazole and
1H-2,5-dimethyl pyrazole; lactams, e.g., .epsilon.-caprolactam and
2-pyrolidinone; ketoximes, e.g., 2-propanone oxime and 2-butanone
oxime. Other suitable capping groups include, but are not limited
to, 3,5-dimethyl pyrazole, morpholine, 3-aminopropyl morpholine,
and N-hydroxy phthalimide.
The isocyanate or mixture of isocyanates of the capped isocyanate
crosslinking agent typically has two or more isocyanate groups
(e.g., 3 or 4 isocyanate groups). Examples of suitable isocyanates
that can be used to prepare the capped isocyanate crosslinking
agent include, but are not limited to, monomeric diisocyanates,
e.g., .alpha.,.alpha.'-xylylene diisocyanate,
.alpha.,.alpha.,.alpha.',.alpha.'-tetramethylxylylene diisocyanate,
and 1-isocyanato-3-isocyanatomethyl-3,5,5-trimethylcyclohexane
(isophorone diisocyanate or IPDI), and dimers and trimers of
monomeric diisocyanates containing isocyanurate, uretidino, biruet,
or allophanate linkages, e.g., the trimer of IPDI.
The capped isocyanate crosslinking agent can also be selected from
oligomeric capped isocyanate functional adducts. As used herein, by
"oligomeric capped polyisocyanate functional adduct" is meant a
material that is substantially free of polymeric chain extension.
Oligomeric capped polyisocyanate functional adducts can be prepared
by art-recognized methods from, for example, a compound containing
three or more active hydrogen groups, e.g., trimethylolpropane
(TMP), and an isocyanate monomer, e.g.,
1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane (IPDI),
in a molar ratio of 1:3, respectively. In the case of TMP and IPDI,
by employing art-recognized starved feed and/or dilute solution
synthesis techniques, an oligomeric adduct having an average
isocyanate functionality of 3 can be prepared (e.g., "TMP-3IPDI").
The three free isocyanate groups per TMP-3IPDI adduct are then
capped with a capping group, e.g., a linear or branched
C.sub.2-C.sub.8 alcohol.
To catalyze the reaction between the isocyanate groups of the
capped polyisocyanate crosslinking agent and the active hydrogen
groups of the active hydrogen functional polymer, one or more
catalysts are typically present in the curable photochromic coating
composition in amounts of from, for example, 0.1 to 5 percent by
weight, based on total resin solids of the composition. Classes of
useful catalysts include, but are not limited to, urethanization
catalysts such as organic tin compounds, e.g., tin(II) octanoate
and dibutyltin(IV) dilaurate, as well as bismuth compounds, zinc
compounds and salts thereof, zirconium compounds and salts thereof,
carboxylates, and tertiary amines, e.g., diazabicyclo[2.2.2]octane.
Mixtures of catalysts can be used.
It should be understood that any of the photochromic coatings known
in the art can be used as the colorant composition in the method of
the present invention. For example, suitable photochromic coatings
can include those described in U.S. Pat. No. 7,189,456 at column 20
line 49 to column 24 line 6, the recited portions of which are
incorporated by reference herein.
The colorant compositions useful in the method of the present
invention optionally further include a solvent. Examples of
suitable solvents can include, but are not limited to, acetates,
alcohols, ketones, glycols, ethers, aliphatics, cycloaliphatic, and
aromatics. Examples of suitable acetates include, but are not
limited to, ethyl acetate, butyl acetate, and glycol acetate.
Examples of suitable ketones include, but are not limited to,
methyl ethyl ketone and methyl-N-amyl ketone. Examples of suitable
aromatics include, but are not limited to, toluene, naphthalene,
and xylene. In one aspect of the present invention, one or more
solvents can be added to each of the first reactant and the second
reactant. Suitable solvent blends can include, for example, one or
more acetates, propanol and its derivatives, one or more ketones,
one or more alcohols, and/or one or more aromatics.
The colorant compositions useful in the method of the present
invention optionally contain additives, such as rheology additives
for flow and wetting, e.g., poly(2-ethylhexyl)acrylate, adjuvant
resin to modify and optimize coating properties, antioxidants
hindered amine light stabilizers (HALS) and ultraviolet light
absorbers (UVA), e.g., hydroxyphenylbenzotriazole,
hydroxybenzophenones, hydroxyphenyl-s-triazines, oxanalides.
Examples of useful antioxidants, HALS, and UVAs include those
available commercially from BASF under the trademarks IRGANOX and
TINUVIN.
As previously mentioned, in the method of the present invention the
colorant composition is deposited on at least one surface of the
optical element in a controlled predetermined pattern using an
inkjet printing apparatus so as to provide a linearly gradient
color pattern on the optical element upon exposure of the optical
element to actinic radiation. The inkjet printing apparatus applies
a colorant composition in the form of extremely fine droplets on
the surface of the optical element. A discharge apparatus
associated with the printing apparatus, such as one or more print
heads, has one or more nozzles associated therewith. Each of the
nozzles is configured to controllably discharge a single droplet of
the composition, either continuously or on-demand. In the on-demand
system, the discharge of droplets is controlled by a controller
having pre-determined droplet discharge profile. For example, the
controller may control the size of the drop (volume of colorant
composition) and the speed at which the drop is formed and
delivered. In some aspects of the present invention, the one or
more print heads may be provided with one or more piezoelectric
elements that provide a mechanism for forming and discharging the
droplets from the one or more print heads. A voltage applied to the
one or more piezoelectric elements, such as a control voltage
determined by the controller, changes the shape of the one or more
piezoelectric elements, thereby generating a pressure pulse in the
colorant composition, which forces a droplet of the composition
from the nozzle. The controller directs one or more print heads to
generate droplets on demand. In this manner, the timing, position,
and volume of colorant composition delivered per unit of area of
the printing surface can be controlled.
In other aspects of the present invention, a thermal ink jet
apparatus can be employed. That is, the one or more print heads may
have at least one chamber including a heater. A droplet is ejected
from the chamber when a pulse of voltage is passed across the
heater, such as a control voltage determined by the controller.
Such a voltage differential causes a rapid vaporization of the
colorant composition in the chamber and forms a bubble. Formation
of the bubble causes a pressure differential within the chamber,
thereby propelling a droplet of the composition onto the coating
surface. The controller directs one or more print heads to generate
droplets on demand. In this manner, the timing, position, and
volume of coating material delivered per unit of area of the
printing surface can be controlled.
Each droplet discharged from the nozzle of the print head is
deposited on the surface of the optical element in the form of a
single dot. Thus, assembly of deposited droplets creates an array
that enables a pattern to be formed. In this manner, all or
portions of the printing surface may be coated. In accordance with
the present invention, when one or more portions of the optical
element surface are printed, a controlled, predetermined pattern
may be formed on the surface, such that, upon exposure to actinic
radiation, a linearly gradient color pattern is observed.
Each print head is in fluid communication with a storage reservoir.
When the printing apparatus has more than one print head,
individual storage reservoirs may be provided for each print head.
Each storage reservoir is configured to store a colorant
composition (or composition free of photochromic material) to be
delivered to the one or more print heads. In this manner, it is
possible to print a plurality of different compositions at the same
time by using a plurality of print heads to generate various
gradient color patterns upon exposure of the optical element to
actinic radiation. Thus, the gradient pattern may be formed on the
surface of the optical element from the deposition of two or more
colorant compositions, or the gradient pattern may be formed from a
single colorant composition applied in one or more successive
layers. Various additional devices, such as heaters, mixers, or the
like, may be associated with each storage reservoir for preparing
the colorant composition prior to delivery to the one or more print
heads. In some aspects of the invention, viscosity of the colorant
composition may be controlled, such as by increasing or reducing
the viscosity of the composition, prior to loading the composition
into the storage reservoir or prior to delivering the composition
to the one or more print heads.
In another aspect, heating of the coating material within the print
head manifold or reservoir also may be used to control coating
viscosity prior to delivering the coating material to the
substrate.
The inkjet apparatus can be comprised of multiple print where each
print head is provided with (i) a different colorant composition,
and (ii) optionally, at least one print head is provided with a
composition free of photochromic material. Each such composition is
deposited on the surface of the optical element in a predetermined
pattern so as to provide a linearly gradient color pattern which
varies in hue and/or color density from one area of the optical
element to another area of the optical element upon exposure of the
optical element to actinic radiation. The composition free of
photochromic material can comprise any of the aforementioned
polymeric compositions used in conjunction with the colorant
composition provided, however, that no photochromic material is
present. With this embodiment, the area of the optical element
provided with the photochromic-free composition will exhibit no
change in hue and/or color density upon exposure to actinic
radiation.
In another aspect of the invention, the inkjet apparatus is
comprised of multiple print heads where each print head is provided
with a different colorant composition. Each colorant composition is
deposited on the surface of the optical element in a predetermined
pattern so as to provide a linearly gradient color pattern which
varies in hue and/or color density from one area of the optical
element to another area of the optical element upon exposure of the
optical element to actinic radiation.
A plurality of print heads may be arranged in an array. The
plurality of print heads may be arranged parallel to one another in
a direction that is angled relative to a direction in which the
optical element is moved relative to the print heads. Offsetting
the print heads at an angle relative to the direction in which the
optical element is moved relative to the print heads allows a
complete coverage of optical elements of various shapes and sizes,
for example, lenses having a convex, concave or segmented surface.
In other aspects, the print heads may be arranged linearly next to
one other in a direction substantially parallel or perpendicular to
the direction in which the optical element is moved relative to the
print heads.
During the printing process, the colorant composition (or a
composition free of photochromic material) may be applied on the
surface of the optical element in a single pass in which the
optical element is held stationary and the one or more print heads
are moved, or in which the optical element is moved and the one or
more print heads are held stationary, or in which both the optical
element and the one or more print heads are moved. The single pass
may be performed using a single print head or multiple print heads.
In some aspects of the present invention, the composition may be
applied on the optical element in two or more passes in which the
optical element is held stationary and the one or more print heads
are moved, or in which the optical element is moved and the one or
more print heads are held stationary, or in which both the optical
element and the one or more print heads are moved. Two or more
passes may be performed using a single print head or multiple print
heads.
The printing apparatus may have a controller for controlling the
operation of the printing apparatus. The controller may be
configured for controlling the printing operations of the one or
more print heads and/or movement operations of the optical element
and/or the one or more print heads. In addition, the controller may
be configured to control the filling and delivery operations of the
colorant composition in the one or more storage reservoirs. For
example, the controller may include a variety of discrete
computer-readable media components for controlling the printing
and/or movement operations. For example, this computer-readable
media may include any media that can be accessed by the controller,
such as volatile media, non-volatile media, removable media,
non-removable media, transitory media, non-transitory media, etc.
As a further example, this computer-readable media may include
computer storage media, such as media implemented in any method or
technology for storage of information, such as computer-readable
instructions, data structures, program modules, or other data;
random access memory (RAM), read-only memory (ROM), electrically
erasable programmable read-only memory (EEPROM), flash memory, or
other memory technology; CD-ROM, digital versatile disks (DVDs), or
other optical disk storage; magnetic cassettes, magnetic tape,
magnetic disk storage, or other magnetic storage devices; or any
other medium which can be used to store the desired information and
which can be accessed by the controller. Further, this
computer-readable media may include communications media, such as
computer-readable instructions, data structures, program modules,
or other data in a modulated data signal, such as a carrier wave or
other transport mechanism and include any information delivery
media, wired media (such as a wired network and a direct-wired
connection), and wireless media (such as acoustic signals, radio
frequency signals, optical signals, infrared signals, biometric
signals, bar code signals, etc.). Of course, combinations of any of
the above should also be included within the scope of
computer-readable media.
A user may enter commands, information, and data, such as
information relating to an art form file of a desired printed
layer, into the controller through certain attachable or operable
input devices via a user input interface. Of course, a variety of
such input devices may be utilized, e.g., a microphone, a
trackball, a joystick, a touchpad, a touch-screen, a scanner, etc.,
including any arrangement that facilitates the input of data, and
information to the controller from an outside source. Still
further, data and information can be presented or provided to a
user in an intelligible form or format through certain output
devices, such as a monitor (to visually display this information
and data in electronic form), a printer (to physically display this
information and data in print form), a speaker (to audibly present
this information and data in audible form), etc. All of these
devices are in communication with the controller, e.g., through an
output interface. It is envisioned that any such peripheral output
devices be used to provide information and data to the user.
In the method for producing the optical element in accordance with
the present invention, the colorant composition (or composition
free of photochromic material) may be leveled to assure a uniform
thickness of the composition which will be or has been deposited on
the surface of the optical element. Leveling may be performed
concomitant with the depositing step, or after the depositing step
is completed. A leveling device may be used to accomplish this.
Furthermore, leveling may be prior, concomitant, or after any
additional post-processing steps after the depositing step but
before the drying step. In some aspects, the leveling step may
include vibrating the optical element. Vibration of the optical
element may be performed linearly, for example in the form of
reciprocal movement along one axis. In other aspects, vibration of
the optical element may be performed linearly along two axes, such
as vibrating the optical element linearly in one plane. In some
aspects, the leveling step may include vibrating the optical
element at a frequency of 10 Hz to 110 Hz. Further, the leveling
step may include vibrating the optical element for 3 seconds to 30
seconds.
Once deposited in a controlled, predetermined pattern so as to form
a linearly gradient color pattern on the optical element upon
exposure to actinic radiation, the colorant composition (or the
composition free of photochromic material) is dried. As used
herein, the terms "dried" or "drying" means that the composition is
exposed to ambient conditions or elevated temperatures in order to
evaporate any solvents present; and/or that the colorant
composition is at least partially cured to promote at least partial
reaction of any reactive components present in the colorant
composition (e.g., in the case of a curable colorant composition).
Both radiation curing and thermal curing are contemplated.
In a particular embodiment of the present invention, the optical
element is a lens, such as an ophthalmic lens, and the linearly
gradient color pattern varies in hue and/or color density from the
bottom of the lens to the top of the lens upon exposure of the lens
to actinic radiation. Further, upon exposure of the lens to actinic
radiation, the gradient color pattern generally has a higher
percent light transmittance at the bottom of the lens than at the
top of the lens.
The optical elements prepared by the method of the present
invention optionally can include one or more layers in addition to
the photochromic composition layer(s). Examples of such additional
layers include, but are not limited to, primer coatings and films
(typically applied to the optical element surface(s) prior to
deposition of the photochromic composition); protective coatings
and films (applied before or after deposition of the photochromic
composition to the optical element surface, including transitional
coatings and films and abrasion resistant coatings and films;
anti-reflective coatings and films; polarizing coatings and films;
and combinations thereof. As used herein, the term "protective
coating or film" refers to coatings or films that can prevent wear
or abrasion, provide a transition in properties from one coating or
film to another, protect against the effects of polymerization
reaction chemicals and/or protect against deterioration due to
environmental conditions, such as moisture, heat, ultraviolet
light, oxygen, etc.
As used herein, the term "transitional coating and film" means a
coating or film that aids in creating a gradual change in
properties or compatibility between two coatings or films, or a
coating and a film. For example, although not limiting herein, a
transitional coating can aid in creating a gradual change in
hardness between a relatively hard coating and a relatively soft
coating. Non-limiting examples of transitional coatings include
radiation-cured, acrylate-based thin films as described in U.S.
Pat. No. 7,452,611 B2, which are hereby specifically incorporated
by reference herein.
As used herein, the term "abrasion-resistant coating and film"
refers to a protective polymeric material that demonstrates a
resistance to abrasion that is greater than a standard reference
material, e.g., a polymer made of CR-39.RTM. monomer available from
PPG Industries, Inc., as tested in a method comparable to ASTM
F-735 Standard Test Method for Abrasion Resistance of Transparent
Plastics and Coatings Using the Oscillating Sand Method.
Non-limiting examples of abrasion-resistant coatings can include,
but are not limited to, abrasion-resistant coatings comprising
organosilanes, organosiloxanes, abrasion-resistant coatings based
on inorganic materials such as silica, titania and/or zirconia,
organic abrasion-resistant coatings of the type that are
ultraviolet light curable, oxygen barrier-coatings, UV-shielding
coatings, and combinations thereof. Non-limiting examples of
commercial hard coating products include CRYSTALCOAT.RTM. and
HI-GARD.RTM. coatings, available from SDC Coatings, Inc. and PPG
Industries, Inc., respectively.
The abrasion-resistant coating or film (often referred to as a hard
coat) can, with some aspects, be selected from art-recognized hard
coat materials, such as organosilane abrasion-resistant coatings.
Organosilane abrasion-resistant coatings, often referred to as hard
coats or silicone-based hard coatings, are well known in the art,
and are commercially available from various manufacturers, such as
SDC Coatings, Inc. and PPG Industries, Inc. Reference is made to
U.S. Pat. No. 4,756,973 at column 5, lines 1-45; and to U.S. Pat.
No. 5,462,806 at column 1, lines 58 through column 2, line 8, and
column 3, line 52 through column 5, line 50, which disclosures
describe organosilane hard coatings and which disclosures are
incorporated herein by reference. Reference is also made to U.S.
Pat. Nos. 4,731,264, 5,134,191, 5,231,156, and International Patent
Publication No. WO 94/20581 for disclosures of organosilane hard
coatings, which disclosures are also incorporated herein by
reference. The hard coat layer can be applied by art-recognized
coating methods such as, but not limited to, roll coating, spray
coating, curtain coating, and spin coating.
Non-limiting examples of suitable antireflective coatings and films
include a monolayer, multilayer or film of metal oxides, metal
fluorides, or other such materials, which can be deposited onto the
articles disclosed herein (or onto films that are applied to the
articles), for example, through vacuum deposition, sputtering, etc.
Non-limiting examples of suitable conventional photochromic
coatings and films include, but are not limited to, coatings and
films comprising conventional photochromic materials.
Although the present invention has been described with reference to
specific details of certain embodiments thereof, it is not intended
that such details should be regarded as limitations upon the scope
of the invention except insofar as they are included in the
accompanying claims.
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